Bis-(anthraquinoneacridono)-pyrenes and process of making them



Patented July 16, 1940 UNITED STATES PATENT OFFICE.

BIS (ANTHRAQUINONEACRIDONO) -PY- R-ENES AND PROCESS THEM OF MAKINGWalter Kern, Sissach, Switzerland, assignor to the firm Society ofChemical Industry in lBasle, Basel, Switzerland No Drawing. ApplicationFebruary 24, 1939, Se-

rial No. 258,347. In Switzerland March 2,

8 Claims.

wherein the two pairs of carbon atoms C102 and 01 02 belong toanthraquinone nuclei C1 and 01' being in a-position and C2 and 02' infi-position, R stands for a pyrene radical, connected with one iminogroup in 3-position and with the other imino groups in one of thepositions 8 and 10 and wherein further each a: is a carboxyl group inwhich the hydroxyl may be replaced by a saponifiable residue, in somecases after treatment with a saponifying agent, and if required treatingthe product thus obtained with an agent having a substituting actionor/and a further condensing action.

The products of the above general formula serving as parent materialsfor the invention can be made, for example, by reaction of 2,mols ofnegatively substituted anthraquinone carboxylic acids in which at leastone negative substituent, for example a halogen, is in ortho-position tothe carboxyl group, for example the l-chloroor1-bromo-anthraquinone-2-carboxylic acid, with 1 mol of di-aminopyrenes;another procedure for making the parent materials is by analogousreaction of ortho-aminoanthraquinone carboxylic acids with negativelysubstituted pyrenes, for example di-chloroand di-bromo-pyrenes. In theanthraquinone carboxylic acids used the hydroxyl of the carboxyl groupmay be replaced by a saponifiable residue, for example an O-alkylresidue, or halogen, or an amido group, in this case it is advantageousto treat the reaction product with a saponifying agent, for examplealcoholic potash, before subjecting it to the action of the condensingagent. The reaction by which the products of the above formula areobtained are conducted in presence of a solvent or diluent, for exampleamyl alcohol, and advantageously in presence of a catalyst and an agentwhich binds acid.

The condensing agent which is caused to act on the reaction product ofthe above formula may for example be an acid condensing agent, such as ahalide of an organic acid, sulfuric acid or a halogen-sulfonic acid.These condensing agents may be caused to acton the said reactionproducts at a raised temperature in the presence of a solvent ordiluent. Halides of carboxylic acids, for

example acetyl chloride or benzoyl chloride, 'are particularly suitablecondensing agents.

The condensation products obtainable "by the invention may be treatedwith agents having a substituting and/or a further condensing actionwhereby further valuable products are obtained; As such agents may benamed for example: halogens and agents yielding halogen, sulfuric acidorganic monocarboxylic acid halides, dicarboxylic anhydrides, aminessuch as aminoanthraquinones' and amines of the benzene or naphthaleneseries, alkylating agents, caustic alkalies and aluminium halides, ifrequired in presence of potassium chloride andsodium chloride.

The new products may be purified by recrys tallisation once or more thanonce from solvents of high boiling point or by conversioninto theirsalts with strong acids or by treatment with oxidizing agents, forexample a solution of an alkalihypochlorite. They may be convertedaccording to known methods-into their leuco derivatives, for exampleinto leuco-sulfuric acid esters.

The products obtainable by the present invention represent;pyrenedi-anthraquinone-diacridones and correspond to the general formulawherein the two pairs of carbon atoms C102 and C1'C2 belong toanthraquinone nuclei, C1 and C1 being in a-position and C2 and C2 ine-position, R

stands for a pyrene radical, connected with one imino group in 3-, withthe corresponding carbonyl groups in 4-, with the other imino-group inone of the positions 8 and 10 and with the other carbonyl group inQ-position.

The products obtainable by theinvention are valuable in some cases asintermediate products and in most cases as dyestuffs; those of theproducts useful as dyestuffs may be used for example for dyeing andprinting vegetable fibres such as cotton.

fast.

The process of the present application is in close analogy with theprocess of the co-pending application Serial No. 169,915 filed October19, 1937. While the said application is chiefly concerned withmono-acridones, the present inven-, tion leads to diacridones of thesame type. Inso far as the following examples may fail to disclose everypossible variation included in the present invention, full informationin this respect may be obtained from the said prior application.

waist They yield dyeings and prints which are The following examplesillustrate the invention, the parts being by weight unless otherwisestated and the relationship between parts by weight and parts by volumebeing that which exists between the kilo and the litre:

Example 1 of nitrobenzene have been distilled. After cooling to 190-200C. (oil bath temperature) 3.6 parts of 3:8-dibromopyrene (obtainable bydibrominating pyrene in carbon tetrachloride as described in Berichtevol. '70, page 930) are added together with 6.5 parts ofl-aminoanthraquinone- 2-carboxylic acid ethyl ester and 0.3 part ofcuprous chloride, and the whole is stirred at the above temperature for20 hours. After cooling the mass is filtered and the solid matter iswashed and extracted with boiling dilute hydrochloric acid to removecopper compounds. There is obtained in good yield a violet-black productsoluble in concentrated sulfuric acid to a red-violet solution andmelting above 300 C. by boiling it for 2 hours with dilute alcoholicpotash it is saponified, whereby a dark powder is produced. This latteris niixed with 84 parts of nitrobenzene and 12 parts of benzoylchloride, the mixture being at first stirred for hour at 110-120 C. andthen kept at the boil for one hour. After cooling to 90 C. the solidmatter is filtered and washed with benzene and alcohol. It is an olivebrown powder soluble in concentrated sulfuric acid to an olivebrownsolution, melting above 460 C. and dyeing cotton in a red-brown vatsomewhat yellowishbrown olive tints of very good properties of fastness.It corresponds with the formula l \l NH 0 If instead of3:8-dibromopyrene a mixture of 3:8- and 3:10-dibromopyrenes is used, thedyestufi obtained also dyes cotton olive tints.

Example 2 2.4 parts of 3:10-dibromopyr-ene (obtainable by dibrominatingpyrene in carbon tetrachloride as described in Berichte, vol. 70, page930), 4.15 parts of 1-aminoanthraquinone-Z-carboxylic acid ethyl ester,0.2 part of cuprous chloride, 1.3 parts of calcined sodium carbonate and1 part of anhydrous sodium acetate are together boiled with 48 parts ofanhydrous nitrobenzene for 12 hours while stirring. After cooling themass is filtered, the solid matter Washed and extracted with boilingdilute hydrochloric acid for removing copper compounds. There areobtained in good yield blackbrown crystals, soluble in concentratedsulfuric acid to a red-brown-violet solution and melting above 300 C.This product is dissolved in concentrated sulfuric acid, reprecipitatedby adding ice, filtered by suction, washed until neutral and saponifiedby boiling for-2 hours with alcoholic potash containing some pyridine,whereby a dark powder is produced. The latter is at first stirred forhour at 1l0-120 C. with 20 parts of nitrobenzene and 2.2 parts ofbenzoyl chloride, and the mixture is finally boiled for one hour. Aftercooling to 90 C. the solid matter is filtered and Washed with benzeneand alcohol. It is a dark powder soluble in concentrated sulfuric acidto a green-yellow solution, melting above 460 C. and dyeing cotton in ared-brown vat pure yellowish olive tints of good fastness. Itcorresponds with the formula What I claim is:

1. Process for the manufacture of condensation products containingnitrogen comprising causing benzoyl chloride to react with products ofthe general formula wherein the two pairs of carbon atoms C102 andC1'C2' belong to anthraquinone nuclei, C1 and C1 being in u-position andC2 and C2 in Bposition, R stands for a pyrene radical, connected withone imino group in 3-position and with the other imino group in one ofthe positions 8 and 10 and wherein further each a: is a substituentselected from the group consisting of COOH, COOalk, CONH2 and C0hal.

2. Process for the manufacture of condensation products containingnitrogen comprising causing benzoyl chloride to react with products ofthe general formula other imino group in one of the positions 8 and 10,and wherein further each a: is a substituent selected from the groupconsisting of COOI-I, COOalk, CONH2 and C0hal.

3. Process for the manufacture of condensation products containingnitrogen comprising causing benzoyl chloride to react with products ofthe general formula NHO wherein each a: is a substituent selected fromthe group consisting of -COOI-I, -COOa1k,-CONH2 and C0hal.

4. Process for the manufacture of condensation products containingnitrogen comprising causing benzoyl chloride to react with products ofthe general formula wherein each :0 is a substituent selected from thegroup consisting of COOH,CO0alk, -CONH2 and -C0ha1.

5. Condensation products containing nitrogen of the general formulawherein the two pairs of carbon atoms 01C: and 01 02 belong toanthraquinone nuclei, C1 and C1 being in oc-DOSitiOIl and C2 and C2 inp-position, R stands for a pyrene radical, connected with one iminogroup in 3-, with the corresponding carbonyl group in 4-, with the otherimino group in one of the positions 8 and 10 and with the other carbonylgroup in Q-position.

v6. Condensation products containing nitrogen of the general formulawherein R. stands for a pyrene radical connected with one imino group in3- and with the corresponding carbonyl group in 4-, with the other iminogroup in one of the positions 8 and 10, and with the other carbonylgroup in 9-position.

'7. The product of the formula 8. The product of the formula WALTERKERN.

